Method for treating calcium sulphate pigments



Patelited Dec.19, 1944 METHOD FOR TREATING CALCIUM SULPHATE PIGMENTS Franklin 1.. Kingsbury, Rnmson. and Frank J. Schultz, 'Foi'ds, N. 1., minors to National Lead Company,-New York, N. Y., a

of New Jersey co p ration No Drawing. Application August 4, 1943,

Serial No. 497,368

8 Claims. (Cl. 108-300) I r adjustable screw legs for leveling the instru- The presentinvention relates to calcium sulphate pigments and to methods for controlling the bodyln Properties thereof. The expression "calcium sulphate pigments as used herein means and includes not only pigmentary calcium sulphate but also composite pigments containing calcium sulphatefor instance, composite titanium dioxide-calcium sulphate pigment.

This application =is' a continuation-inpart of ounce-pending Serial No. 383,548, filed March 15, 1941, now Patent No. 2,341,994, dated Feb. 15, 1944, for improvements in Methods for treatin calcium sulphate pigments.

tance of the plunger's fall through the paint.

The bodying properties of a pigment may be film-forming compositions particularly flat wall paints for the. purpose of increasing the consistency of the composition. Bodying agents most commonly used are water and soap solu-' tions. The extent of bodyin i. e. increase in consistency, developed by the bodying agent will vary depending upon the nature of the pigment portion of the film-forming material, and it has been found in connection with titanium dioxidecalcium sulphate pigments that'diflferent batches although containing the same relative proportions of titanium dioxide and calcium sulphate give different bodying effects when incorporated in film-forming vehicles .to which a bodying agent is added.

Itwill be appreciated that the control of the bodying properties of calcium sulphate pigments presented a problem of considerable importance to the industry. The present invention pro vides a simple and effective solution of that problem.v

A proper understanding of the invention necessitates a brief consideration of what is meant by the term consistency as applied to a film-forming composition, e. g., a paint, and the method of determining it. The consistency of,

'for instance, a paint has' been defined as its resistance to deformation or flow which resistance may be due to viscosity or to plasticity. The method of determining consistency which was employed to obtain the results hereinafter reported was as follows:- l An instrument sometimes called a consistometer or "mobilometer was employed. Thisinstrument consists of a base plate provided with of volatile thinner.)

ment. 9. tall cylinder supported by the base plate for receiving thepalnt to be tested, a plunger having a perforated disc at one end and: a weight pan at the other. and a guide bracket-also supported by-the base'for guiding the fall of the plunger. The cylinder is provided with a mark on its inner surfaces to fix the level to which it is to he filled with paint. The plunger rod has two marks 5 cm. apart which determine the dis- The 'disc is perforated with holes about 1:

inch in diameter. 1

The procedure for testing the pigment involved weighing 120 grams of the pigment into a porcelain enamel cup. A suflicient amount of film-forming. vehicle was added to form a Paste suitable i'or grindingwhen the pigment-vehicle mixture is worked; together, The paste was weighed in order to ascertain the weight'of vehicle used. ,It was then runv .once through a three-roll laboratory mill and after this treatment cut down with additional vehicle so that the paint contains 56 per cent. pigment and 44 per cent vehicle. tang-linseed oil mixture containing per cent grams of the paint so prepared were weighed into a suitable vessel and 0.5 cc. of a'2.0 per cent cobalt naphthenate drier added thereto.

The bodying of a paintprepared as above described was efiected by adding to thelOO a grain sample 1.5 cc. of a soap solution after the drier had been incorporated. The soap solution was mixed in hy,stirring, for instance, using a low speed forked stirrer turning at 750 R. P. M., for exactly 6 minutes. After stirring, the paint was allowed to stand to permit the escape of entrapped air and to allow the body to develop which requires a minimum of one-half hour. (The soap solution was prepared by dissolving 1 part by weight of a neutral soap, e. g. Ivory soap flakes, in 99 parts of distilled water and adding thereto parts by weight of ethyl alcohol.) Indetermining the bodying characteristics of a pigment, determinations" were made both on the paint containing no soap solution (The vehiclewas a processed the paint was poured into the cylinder up to the inner mark. The plunger was fastened in the guide bracket while holdingit above the level of the paint. The weighting pan and sufllcient ad;-

mined value-"was placed on the plunger and the perforated disc immersed in the paint to a depth so that the lower mark on the stern of the plunger was just visible above the collar of the guide bracket. The plunger was held in this position for exactly seconds. The plunger was then allowed to fall through the paint, the time required for the upper markon the plunger stem to reach the collar of the guide bracket bein taken by a stopwatch. (The weight of the plunger plus pan plus added weight for testing paints containing no bodying agent was 20 grams; that for bodied paints grams or, if necessary, because of the heavy body 75 grams W or even 125 grams.)

The above test was carried out at 70 F.i2 F. and a relative humidity of The results obtained were expressed as gramseconds which is the product of multiplying-the weight of the plunger plus pan plus added weight by the time in seconds required for the plunger to fall the distance between the two marks, i. e.,

5 cm. (For a coniplete discussion of consistency of paints and methods and apparatus for evaluating consistency the reader is referred to chapter 17, page 561 et seq. Physical and Chemical Ex amination of Paints, varnishes, Lacquers and Colors by Dr. Henry'A. Gardner, eighth edition, 1937, distributed by the Institute of Paint and Varnish Research, Washington, D. C.)

From the foregoing it will be appreciated that a pigment having undesirable bodying characteristics will exert a detrimental effect on the finished surface coating compositions containin it. Very often it is ,found that the undesirable bodying characteristic is in the nature of a tendency toward excessive bodying and there is need for some means of lowering thebodying tendency. The consistency of the paint obtained after the addition of the bodying agent, usually water or a soap solution is known as "bodied consistency, that of the untreated paint as "unbodied consistency." Thus, it is an object of the present invention to provide means for lowering the bodying tendency of calcium sulphate pigments. It is another object of the present invention to provide means for treating pigmentary calcium sulphate and composite titanium dioxide-calcium sulphate pigments so that paints may be prepared from such treated pigments possessing any predetermined consistency. These and other objects of the invention will become apparent from the present description.

In its broadest aspect the invention contemplates determining the bodying tendency of a calcium sulphate pigment by testing a sample of the pigment and if it be desired to lower the bodying tendency to admix with the pigment a small amount of an organic aliphatic amine.

Thus, according to the invention, it has been found that the addition of small amounts for ethylene amines, such as ethylene diamine,

Nmcmcmm diethylene triamine,

NH2.CH2.CH2.NH.CH2,CH 2;NH2 triethylene tetramine,

NH2.CH2.CH2.NH.CH2.CH2.NH.CH3.CH2 NH2 etc., as well as aliphatic alcohol amines which contain less than 8 carbon atoms, such as isopropanol amine. CHa.CHOH.CH.NHz, triethanolpurposes the two extremes.

amine, N(C2H4OH)3, etc., will lower the bodying tendency of calcium sulphate "pigments.

The amount of amino-compound to be admixed with the calcium sulphate pigment will vary depending upon the amount of lowering in bodying tendency desired. Amounts between about 0.05 per cent and about 2.0% cover'for all practical Ordinarily, amounts of treating agent-ranging from about 0.1 per cent to about 1.0 per cent are effective, a preferred range being from about 0.1 per cent to about 0.5 per cent, calculated on the weight of the pigment.

The amino-compound may be admixed with pigment particles in any convenient manner. If the amine is a solid it may be incorporated with the dry finished pigment by intimate mixing means. If the amine is a liquid, or if a solution of solid amine is employed, it may be sprayed upon the dry pigment and, if necessary, the solvent may be removed'by evaporation. If the amine is. to be added to a pigment which in the course of manufacture is subjected to a milling treatment, either wet or dry milling or both, the addition may be made prior to,.during, or after such milling treatment. If the pigment requires a calcination treatment the amine should always EXAMPLE I An unmilled composite titanium dioxide-calcium sulphate pigment, consisting oi 30 per cent TlOa and '70 per cent CaSOa was sprayed with an aqueous solution of triethylene tetramine,'

and then tumbled and dried at C. to C. to evaporate the water. The amount or treating agent added was calculated to be 0.26 per cent based on the weight of the pigment. The treated and dried product was then pulverized in a Raymond mill, air separated and then passed through a hammer mill to further insure an even distribution of the amine.

This pigment treated according to our novel process was superior to a similarly milled and disintegrated untreated pigment in respect to mixing, dispersibility, viscosity, drying, color stability and gloss when incorporated into organic coating vehicles.

When the coating compositions prepared with the treated and the untreated composite pigment were bodied by the addition of a small amount of water it was found that our novel water sensitivity reducing treatment had lowered the consistency of the paint about 50 per cent, as shown by the results obtained from tests carried out in the modifled Gardner mobilometer referred to above.

To a dry milled composite titanium dioxidecalcium sulphate pigment obtained by co-precipitation, 30 per cent TiOz-IO per cent 08.804. was added at a uniform rate in a screw conveyor as the pigment was being fed to a hammer mill, 0.2 per cent diethylene triamine,

NI-Iz.CHz.CHz.NH.CI-Iz.CIh.NI-Ia based on the weight of the dry pigment.

when incorporated into organic coating vehicles.-

When a small amount of bodying agent (water) was added to a fiat wall paint fbrmulated with treated and untreated pigment, it was found that, because of reduced water sensitivity brought about by our novel treatment, the viscosity or consistency of the paint was reduced about 70 a per cent.

After long storage in cans it was found that the untreated pigment had settled out to a hard cake which could be redispersed in the vehicle only with great difliculty. The paint prepared with the amino-treated pigment, however, had settled to a soft, easily redispersible cake.

EXAMPLE III A composite titanium dioxide-calcium sulphate pigment, 30 per cent TiO-70 per cent CaSO obtained by wet mixing prior to recalcination, wasJnilled in an edge runner mill with 0.4 per cent tetraethylene pentamine,

NH2(CH2.CH2.NH) aCHaCI-IaNH-z based on the weight of the pigment followed by disintegration in a hammer mill. d

The same pigment similarly milled and disintegrated, but not treated according to our process, was compared'as to pigment properties with the treated pigment. It was found that as in Experiments Nos. I and II the treated pigment,

when incorporated into coating composition vehicles, was superior to the untreated in respect to consistency, dispersibility, drying, color stability and gloss characteristics.

E When a small amount of bodying agent (wa-' ter) was added to flat wall paints formulated formulated therewith. a

EXAMPLE W A calcium sulphate, prepared by running a lime slurry into excess concentrated sulphuric acid followed by steaming until the hydrated portion of the calcium sulphate was completely converted to the anhydrous form, was deliqu'ored,

washed and dried and then calcined at about This calcium sulphate anhydrite was mixed with unmilled TiOz in the proportion 30 parts TiO2 to 70 parts CaSO4 and then mixed with 0.5% of mixedisopropaholamines, then milled in an edge runner mill and passed through a hammer mill. The same mixture without the amine treatment was similarly milled and disintegrated.

The treated and the untreated pigments were then used in the formulation of flat wall paints whereto, for the purpose of increasing the-consistency a, small amount of bodying agent, water, was added.

\ It was found that the paint formulatedwith' the untreated pigment became so 'viscous that it could not be applied with the brush. The paint formulated with the amine-treated pigment according to our process however developed a desirable consistency. other properties such as dispersibility, drying, color stability of the dried film and gloss characteristics, as well as settling characteristics also were superior in case of the treated pigment.

I EXAMPLE V Calcium sulphate anhydrite, prepared and calcined as described under Experiment IV above, was milled in an edge runner millwith 0.3 per cent diethylaminoethanol, (C2Hs)2:N.C2H4.OH,

followed by disintegration in a hammer mill.

The milled, treated and disintegrated calcium sulphate anhydrite, when used as an extender in organic coating vehicles, and particularly when incorporated in flat wall paints bodied with a-small amount of water produced coating compositions, which were markedly superior to similar coating compositions formulated with untreated calcium sulphate extender, in respect to consistency, dispersibility, workability, drying and color stability of the dried film, as well as settling characteristics on storage in containers.

The amine treatment also produced in the coating compositions, excluding the flat wall paints, an improved gloss and gloss retention of the dried film.

The following table presents data with respect to the efliciency of certain amino-compounds in lowering the bodying tendency of composite titanium dioxide-calcium sulphate pigment having a bodying tendency determined in the manner above described of 2400.

From the foregoing it will be seen that when calcium sulphate pigments are treated with amino-compounds according to the present invention there results not only a lowering of the bodying tendency but the pigment is also improved in other respects, particularly, as to mixing properties and dispersibility in various vehicles, drying properties, color stability and gloss retention of surface coating compositions containing the pigment.

From this description of the invention it will br seen that by means of the present invention the bodying tendency of calcium sulphate pig-' ment may be controlled as desired. Pigments prepared according to the invention are particularly adapted for use in surface coating compositions, especially fiat wall paints for interior flnishes. They also are excellently adapted for use in inks, paper, rubber, plastics and similar compositions in which suchpignients are incorporated. p y

We claim:

1. Method for lowering the paint bodying.

ment a small amount of an aliphatic alcoholic amine containing less than eight carbon atoms.

2. Method according to claim 1 wherein the aliphatic alcoholic amine is triethanol amine.

3. Method'acccrding to claim 1 wherein the aliphatic alcoholic amine is diethylaminoethanol.

Method according to claim 1 wherein the aliphatic alcoholic amino-compound is a. mixture of isopropalnol amines.

5. Method according to claim 1 wherein the pigment is pigmentary calcium sulphate.

6. Method according to claim. 1 wherein the pigment is composite titanium dioxide-calcium sulphate pigment. 

